Rosin alkylation



Fatente Jan. 1, 34

RGS M s1 7 Donald Price, New York, N. K, asslgnor to National GilProducts @ompany, Harrison, N. 3., a corporation of New Jersey NoDrawing. Application September 30, 1942,

- serial No. 4.60.233

12 Claims.

I Price and May, Serial NOS. 410,778 and 410,779,

filed September 13, 1941, now U. S. Patents 2,376,381 and 2,376,382,respectively, to condense rosin and analogous substances withalkyl-yielding compounds. The resulting condensation products may beused for many purposes, for instance, asadditives to lubricants, asplasticizers or, when sulfonated, as surface-active agents and the like.The above-mentioned applications describe the condensation of thesematerials by the use of condensing agents such as sulfuric acid, oleumand Friedel-Crafts catalysts. These procedures are somewhat expensiveand troublesome in that the reagents used as condensing agents are lostin the process, large quantitie of corrosive fumes are evolved and thereactions must be conducted in corrosion-proof vessels. Likewise, whensulfuric acid or its derivatives are used as condensing agents, it isimpossible to avoid the formation of sulfonated products, which areundesirable for many purposes.

Accordingly, it is an object of this invention toprovide an improvedprocess for condensing rosin with alkyl-yielding substances which may becheaply and easily carried out. Another object is to provide such aprocess in which the catalyst used to promote the reaction is recoveredwithout substantialloss.

Still another object is to provide a condensation process of this typewhich will not involve the use of corrosive chemicals orthe developmentof noxious fumes.

A further object is to provide a condensation process which will avoidany sulfonationor other adverse chemical action upon the compound beingproduced.

Still another object is to provide a process which may be carried out ina continuous manner.

The above and other objects are achieved in accordance with thisinvention by reacting a rosin compound (such as methyl abietate) with analkyl-yielding agent (such as lauryl alcohol) in the presence ofahydrosilicate catalyst at moderately elevated temperatures. Thereaction mixture, which may be separated from the catalyst bydecantation or filtration, consists of condensation products of therosin compound with the alkvl-yielding agent, together with theunreacted constituents. The condensation product may be separated fromthis mixture by any suitable means, for instance by distillation. Thecondensation product so isolated 'may be used as such for anyappropriate purpose or may be further treated as by sulfonation,nitration, hydrogenation, or the like.

Hydrosilicate catalysts suitable for use in this process include anyhydrosilicate having a. large capillary surface and in general includethe surface-active clays, preferably such clays which have been preparedby acid extraction or otherwise so as to remove all constituents exceptthe active hydrosilicates. Natural surface-active .clays are exemplifiedin fullers earth, Floridin, bentonite and the like. Examples of thepre-.

ferred acid-activated clays are those products sold under. the tradenames of Tonsil, Retrol,

Frankonit, "Superfiltrol and Filtrol.

Rosin compounds suitable for use as starting materials in this processinclude in general those substances derived from the gymnospermtreeswhich are' characterized by the trialicyclic nucleus of rosin. The rosinnuclei in the rosin compounds employed in the process of this inventionmay be hydrogenated, dehydrogenated or may occur in disproportionatedmixture. The rosin compounds suitable for use as starting materials inthe process of this invention include rosin materials not containing anycarboxyl groups, acidic rosin materials containing free carboxylic acidgroups and acidic rosin materials, the'carboxyl groups of which havebeen removed or blocked, as by esteriflcation. Examples of resinmaterials not containing carboxylic groups include rosin oils,'decarboxylated rosin and the fossil resins. Examples of acidic rosinmaterials which are adapted for use in the process of this inventioninclude rosin, hydrogenated, dehydrogenated and disproportionated rosin'or the acids characteristic thereof, such, for example, as abietic.Pimaric, sapinic and the like acids. Further, the resinous materialsderived from tall oil contain large quantities or compounds having therosin nucleus and may be used in place of rosin. These acidic materialsmay be preliminarily treated so as to remove or block the carboxylicgroups, for instance, by any decarboxylating process or byesterification with an alcohol such as methyl, ethyl, propyl and butylalcohols, as

well as other alcoholic substances such as the polyhydric alcohols.Examples of suitable esters are the methyl, ethyl, propyl, butyl andlike esters of abietic, dihydroabietic, dehydroabietic, pi-

maric and sapinic acids, or mixtures of these acids. Hereinafter all theforegoing and allied substances will be designated rosin compounds.

Coming now to the alkyl-yielding compounds obtained by the employment ofalkyl-yielding compounds containing upwards of 8 carbon atoms, as theresulting condensation products are admirably adapted forlubricant-blending and (when sulfonated or phosphonated) forsurface-active agents in aqueous media. Of the several types ofallgvl-yielding agents, the olefins and alcohols are preferred, as thesematerials react smoothly, do not produce corrosive fumes, and arecheaply and readily procurable. Suitable alcohols may be chosen from thelower alcohols such as methyl, ethyl, isopropyl and the like, but moreuseful products are obtained from alcohols containing preferably upwardsof 8 carbon atoms such as octyl, 2-ethyl hexyl, lauryl, myristyl, cetyland-like alcohols, or mixtures of such alcohols formed by the reductionof the fatty acids derived from variousoils, such as coconut oil,babassu oil, soyabean oil and the like. Suitable alkenes andcycloalkanes are those containing preferably upwards of 8 carbon atoms,such as octylene, 'diisobutylene, ethylcyclohexane. dodecylene and thelike, but lower homologues, may be used if desired. The alkenes may beobtained by dehydration of corresponding alcohols. Both the alkenes andcycloalkanes may be derived from petroleum products or from thecracking,

polymerization and dehydrogenation products ofpetroleum and petroleumgases.

Suitable alkyl halides for furnishing the alkyl constituent in thereaction above described include alkyl chlorides preferably containingupwards of 8 carbon atoms, such as the octyl, nonyl, decyl, undecyl,lauryl and myristyl chlorides, although lower chlorides may be used ifit is desired to produce products containing lower alkyl groups. Insteadof the pure compounds, mixtures of suitable chlorides may be employed,such as the mixtures of chlorides obtainable by the chlorination ofpetroleum distillates containing alkyl chains of the requisite length.Instead of chlorides, obviously other corresponding halides may be used.

The condensation of the rosin compound and the allgvl-yielding agent isbrought about by mixing these reactants together with the hydrosilicatecatalyst, and heating to moderately elevated temperatures between about75 C. and about-225 C. for between about 1 and about 8 hours. The amountof alkyl-yielding agent will vary, depending on the characteristicsdesired in the final condensation roduct. In general between about 1 moland 3 molsof alkyl-yielding agent will be employed for each mol of therosin compound with which it is to be condensed. If it is foundconvenient, the reactants may be diluted with a suitable inert solventsuch as a petroleum solvent. The pressures under which the reaction iscarried out will of course be adjusted tothe characteristics of thematerials being reacted, being raised to above atmospheric pressure, ifnecessary, to prevent the escape of the essential reactants. Likewise,the reaction may be carried out under a reflux condenser, which mayoptionally be equipped with a trap to prevent the return of undesiredend products such as water. The reactions occurring during thecondensation are of an obscure nature and are believed to consistprincipally of the addition of the alkyl groups from the alkyl-yieldingsubstance to the rosin nucleus. This is indicated by the relatively lowboiling points and oily character of the products. However, a certainamount of rearrangement may take place within the rosin nucleus itself,and certain minimal quantities of rosin may be condensed. Accordingly,the applicant does not wish to be bound by any particular theory as tothe course of the condensation reaction and the products" resulting willhereinafter be designated condensation products without indicating whatthe exact nature of these. products may be. ;-In general these productswill have the some properties as were observed in the condensationproducts disclosed in the above-mentioned applications of Price'and May,being suitable for additives to lubricating compositions and beingsusceptible of sulfonation, phosphonation, etc. to yield surface-activeagents which may be used as detergents, scouring agents, wetting agentsand the like, according to the nature of the materials condensed and theconditions of condensationand sulfonation.

The process is admirably adapted. to continu ous operation since thecatalyst (activated clay) is a solid and readily separable from thereacting materials. Thus. the catalyst may be suspended in a flowingstream of the rosin material and alkyl-yielding agent, and thesuspension passedthrough a heated reaction column to bring about thecondensation of the rosin material and'allrylyielding agent. Thecatalyst may be filtered from the reaction mixture emerging from thecolumn, and recycled. p

With the above general discussion in mind there are given herewithspecific examples of the I practice of this invention. All partsgivenare by weight.

EXAMPLE I Caprylated rosin oil A. reflux condenser was provided forreturning the unreacted materials distilled from the reaction mixture,which reflux condenser was equipped with a water trap to avoid thereturn of the-water split out from the reactants. Thereafter the reaction mixture was filtered from the catalyst while still warm andconsisted of a pale yellow viscous oil. This oil was then subjected tofractional distillation and a small amount of lower boiling materialdistilled off at about (1., leaving 36:

parts of the alkylated product.

EXAMPLE II Caprylat'ed methyl abietate EXAMPLE III Caprylated methyldehydroabietate 32 parts (1 mol) of methyl dehydroabietate (Galex methylester manufactured by the G. 8: A.

Laboratories, Savannah, Ga), 13 parts, (1 mol) of capryl alcohol, and2.5 parts of a commercial aetivated bleaching clay ("SuperfiltroPmanufactured by the Filtrol Corporation of California)v were heated for6 /2 hours with reflux attemperatures ranging between and C. Thereaction mixture was filtered and subjected to fractional distillationas described above in Example,

I. 35 parts of a pale yellow oily condensation product were recovered. I

Caprylated methyl dehydroabietate 30 parts (1 mol) of dehydroabieticacid (Galex, a product manufactured by the G. 8:

A. Laboratories) and 13 parts of capryl alcohol were refluxedfor '6hours at temperatures ranging between 170 and 185 C. in the presence of.

2.5 parts of an activated hydrosilicate. The reaction mixture wasthereafter worked up exactly as described in the previous examples andthere were recovered 21 parts of a dark red oil which was completelysoluble in 10% sodium hydroxide solution.

LE V Capwlated rosin oil 30 parts (1 moi) of a rosin oil having an acidnumber less than 5, 13 parts of capryl alcohol and 2.5 parts of anactivated hydrosilicate were refluxed for 6 hours. The reaction productwas illtered to remove. the activated hydrosilicate', leav ing a paleyellow oil.

LE VI kylated methyl abietate 32 parts (1 mol) of methyl abietateand 25parts of a mixture of terminally-unsaturated mono-olefinic compoundsderived from petroleum and having an average molecular weightcorresponding to about 12 carbon atoms were refluxed for 8 hours with2.5 parts of Superfiltrol at-temperatures ranging between 170 and 220'30 parts of a neutral rosin oil, parts or .dodecyl chloride and 3 partsSuperflltroP' were distilled; Y elding a light yellow, viscou on 1.; I

ling in the rangebetween 152 and 172 C., under 1 mm. pressure, leavingbehind a solid residue Condensate of rosin 'oil and diisobutylene 60parts of a rosin oil having less than 5% free rosin acids and 22 partsor diisobutylene were refluxed for 4 hours in the presence of 5 partsoilv Superfl1trol. Thereafter'the reaction mixture was filtered toremove the Superflltrol, leaving 73 parts of a straw-colored oil.

v Exem t-a m Dodecylated rosin oil stirred and refluxed at temperaturesbetween 225 and 230 C. for 5 hours. H01 was evolved and absorbed in KOHsolution. There resulted 41 grams of'a pale yellow, fluorescent, oilycondensation product.

' Emmi-am Alkylated methyl abietate A petroleum fraction consistingpredominantly of 12 carbon atom chains was chlorinated at tem peraturesbetween 90 and 100 C. to the extent C. The reaction mixture was filteredto remove I the Superflltrol and then subjected to distillation at 170C. to remove asmall amount of low boiling material, leaving acondensation product consisting of a red oil.

1 EXAMPLE V11 n Decylated rosin oil 30 parts (1 mol) of neutral rosinoil, 15 parts (1 mol) of n-decanol and 2.5 parts of Superflltrol" wererefluxed for 4 /2 hours at temperatures ranging between 220 and 228 C.Upon working up the-reaction mixture as described in Example I therewere obtained 36 parts of a pale yellow, fluorescent oil.

LE VIII Octylated rosin oil 11 parts of octylene-l were substituted forthe 15 parts of n-decanol in the procedure of Example VII. The resultantcondensation product obtained consisted of a pale yellow, viscous oil.

Exes-mm: m

Octylated methyl dehydroabietate 157 parts (1 mol) of methyldehydroabietate (Galex methyl ester"), 56 parts (1.3 mole) of of'about25%. 88 parts of the chlorinated petroleum fraction prepared as justdescribed'and 30 parts of methyl abietate were mixed with 3 parts ofSuperflltrol and the mixture was refluxed for 6 hours at temperaturesranging between 225 and 230 C. HClwas evolved during the reaction,' andabsorbed as in Example XI. The reaction.

mixture was then distilled and 54 parts of unreacted hydrocarbons cameover inthe range between 190 and 220 C., leaving behind 53 parts of anoily condensation product.

EXAMPLE i=1 1;

' Alkylated methyl dihydroabz'etate 30 parts of methyl dihydroabietate(Galex methyl ester") were- 'substituted for the methyl abietate in theprocedure of Example m1. There were obtained 43 partsof an oilycondensation product.

EXAMPLE XIV 2 Ethyl hexyl derivative of rosin oil 30 parts (1 mol) of arosin oil having an acid number less than 5, 13 parts (1 mol) of 2-ethyl hexanol and 3 parts of Superfiltrol were refluxed with stirring attemperatures ranging between 130 and 140 C. for 4 hours. The reactionmixture was filtered while still hot to remove the Superfiltrol." Thefiltered mixture was subjected to distillation up to a temperature of200 octylene and 20 parts of superfiltror were C. to remove the volatileunreacted material, leaving behind 32 parts of a light yellow, mobile,oily condensation product.

' EXAMPLE XV Caprylated diethylene glycol diabietate 34 parts ofdiethylene glycol diabietate (Flex alyn, a. product manufactured by theHercules Powder Co.) parts of capryl alcohol and 6' parts of activatedclay (SuperfiltrOl) were mixedand refluxed at temperatures rangingbetween 130 and C. for 6 hours. A trap was provided to prevent thereturn-of water with the reflux. The reaction mixture was then filteredto remove the activated clay and subjected to vacuum distillation toremove the excess unreacted material. 48 parts of a crude product wereobtained.

' ExAurLsxVI i C'aprulated abietic acid 20 parts (1 moi) of pure abieticacid prepared 6 as described in the Journal of the American ChemicalSociety, 44, 1333 (1922) were dissolved in 100 parts (9 mols) of caprylalcohol, and 6 parts of Superfiltrol were added to the solution. Themixture was then refluxed under a column provided with a water trap. Atthe end .01 10 hours refluxing, the theoretical amount or: waterhad beeneliminated and caught in the trap, and-the reaction mixture was cooledand filtered to remove the Superfiltrol. The filtered mixture wasdistilled to remove the-excess octylene (derived by dehydration of thecapryl alcohol); leaving behind 23 parts of an oily residue. Thisresidue was subjected to vacuum distillation at 3 mm.

ated abietic acid is 414); and 5 parts of a plastic resin coming over inthe range 21i )-220 C.

Exmrta XVII Tall oil alleviation 50' parts of a tall oil, the acidgroups of which had been esterified with glycerin, were mixed with 100parts of capryl alcohol and 6 parts offSuperfiltrol.

The mixture was mechanically stirred and refluxed for 10 hours at 180 C.under a condenser provided with a.v water trap. Thereafter, the mixturewas filtered to remove the Superfiltrol and evaporated at atmosphericpressure up to a temperature of 230 C. to strip oi! the unreactedmaterial, leaving a residue of 53 parts of a mobile oil.

From a consideration of the foregoing examples, it will be seen thatthis invention provides a process for condensing rosin materials withalkylyielding agents which does not involve the use of corrosivechemicals or the loss of any of the reactants, since the catalyst may berecovered in-its original, unchanged form by mere mechanical separation.Further, inmost cases the process may be carried out in apparatus of theordinary and cheap construction materials which need have no particularresistance to corrosion. Still further the reactions proceed smoothlyand result in high yields of homogeneous products suitable for manytechnical applications. I

Itheret'ore claim:

1. A process of producing an alkylated rosin compound which comprisesalkylating, in the presence of an activated hydrosilicate catalyst, aresin compound selected from the group consisting of rosin, hydrogenatedrosin, dehydrogenated rosin. disproportionated rosin, abietic acid,pimaric acid. sapinic acid, and the esters and decarboxylation productsthereof, with an alirylyielding compound capable of alkylating saidrosin compounds.

2. A process "of producing an alkylated rosin compound which comprisesalkylating, in the presence of an,activated hydrosilicate catalyst, arosin compound selected from the group consisting of resin. hydrogenatedrosin, dehydrogenatedrosin, disproportionated rosin, abietic acid, pi-

maric acid, sapinic acid, and the esters and decarboxylation productsthereof, with a monohydric alcohol.

3. A process of producing an allwlated rosin compound which comprisesalkylating, in the presence of an activated hydrosilicate catalyst, arosin compound selected from the group consisting of rosin, hydrogenatedrosin, ,dehydrogenated rosin. disproportionated rosin, abietio acid,pimaric acid, sapinic 'acid, and the esters and decarboxylation productsthereof, with an olefin.

4. A process of producing an alkylated rosin compound which comprisesalkylating, in the presence of an activatedhydrosilicate catalyst, arosin compound selected from the group consisting of rosin, hydrogenatedrosin, dehydrogenated rosin, disproportionated rosin, abietic acid,pimaric acid, sapinic acid, andthe esters and decarboxylation productsthereof, with an alkyl halide.

maric acid, sapinic acid, and the esters and decarboxylation productsthereof, with an aimlyielding compound containing at least 8 carbonatoms and being capable of alleviating said rosin compound.

6. A process of producing an alkylated rosin compound which comprisesalkylating, in the presence of an activated hydrosilicate catalyst, arosin compound selected from the group consisting of rosin, hydrogenatedrosin, dehydrogenated rosin, disproportionated rosin, abietic acid, pi-

maric acid, sapinic acid, and the esters and decarboxylation productsthereof, with a monohydric alcohol containingat least 8 carbon atoms.

7'. A process of producing an alkylated rosincompound which comprisesalkylating, in the presence of an activated hydrosilicate catalyst, arosin compound selected from the group consisting of resin, hydrogenatedrosin, dehydrogenated I rosin, disproportionated rosin, abietic acid,pimaric acid, sapinic acid, and the esters and decarboxylation productsthereof. with an olefin containing at least 8 carbon atoms.

8. A process of producing an alkyiated rosin compound which comprisesalkylating, in the presence of an activated hydrosilicate catalyst, a

rosin compoundselected from the group consist-,

which comprises alkylating resin, in the presence of an activatedhydrosilicate catalyst, with a monohydric alcohol containing at least 8carbon atoms.

11. A process of producing an alkylated rosin which comprises alkylatingrosin, in the presence of an activated hydrosilicate catalyst, with anolefin containing at least 8 carbon atoms.

12. A process of producing an alkylated rosin oil which comprisesalkylating. rosin oil, in the presence of an activated hydrosilicatecatalyst, with a monohydric alcohol containing at least 8 carbon atoms.

DONALD BEIGE.

